Heavy metals in the Rosetta estuary of the Nile and the adjoining Mediterranean waters: evidence of removal of dissolved heavy metals from waters as a result of possible binding to suspended matter

The Rosetta estuary was partially separated from the Rosetta branch of the Nile by Edfina Barrage, which controls the Nile discharge into the Mediterranean Sea. The study area covers the Rosetta estuary (lotic environment) and the adjoining seawaters (lentic environment) to investigate the local and seasonal distribution of dissolved and particulate copper and zinc, as well as dissolved cadmium in this estuary and to illustrate its influence on the distribution of these metal forms in the inshore seawaters. Besides, emphasis on the removal of dissolved heavy metals from waters by their adsorption onto suspended matter (SM) was also considered. Contrary to particulate copper (PCu), the vertical values of dissolved copper (DCu) decreased generally with depth. Planktonic scavenging and regeneration processes might determine the vertical profiles of the copper forms. The copper data suggest that the surface sources of DCu exceeded the bottom sources, contrary to the sources of PCu. The markedly high and maximum seasonal averages of DCu in the estuary and inshore seawater in July inspite of the high uptake in summer possibly reflect higher amounts of humic materials. The lowest seasonal average value of DCu in the inshore seawater in January suggests removal of copper in presence of maximum value of SM during highest discharge. The highest regional average of DCu at the estuarine mouth coincided with desorption process during mixing of the fresh and salt waters. The vertical values of dissolved zinc (DZn) and particulate zinc (PZn) showed irregular variations and their high concentrations in the surface of the estuarine and inshore seawater indicate possible land-based sources. The high bottom DZn values, however, resulted from its contribution from the interstitial water of the sediments. The data suggest that the surface sources of DZn exceeded the bottom sources and PZn showed the opposite trend in the open sea area. In the estuary, the maximum seasonal average value of DZn accompanied by the lowest seasonal average of PZn in April inspite of the high uptake in spring suggest that desorption was the dominant process. The minimum regional averages of both zinc forms at the estuarine opening and the highest average of PZn near Edfina Barage are correlated with the amounts of SM, which decreased toward the estuarine mouth. The vertical values of dissolved cadmium (DCd) were much lower in the estuary than the other metals. They showed in both environments irregular variations with depth. The bottom maximum value of DCd can be attributed mainly to contamination from the sediments. There was a distinct seasonal variation of DCd. The minimum seasonal average value of DCd in the estuary in April seems to be caused by its specific binding to living plankton found in abundance. The minimum regional average of DCd value was found at the estuarine mouth. The decrease in Cd concentration due to removal from dissolved state is most pronounced in the early stage of mixing. The correlation coefficients of DCd were positive with salinity and negative with SM, indicating that Cd increased seaward. Statistical correlation between Cd and Zn concludes that the factors affecting their distribution are generally the same.     

Biogeochemical behaviour of Cd, Cu, Pb and Zn in the Scheldt estuary during the period 1981–1983

Cu, Zn, Cd and Pb have been analysed in suspendedmatter and water samples from the Scheldt estuary,collected during five cruises between May 1982 and May1983. In order to evaluate the overall metal behaviourin the estuary, continuous longitudinal profiles ofthe total, the particulate and the dissolved metalconcentrations are discussed in relation to variousspecific physico-chemical parameters. By means ofcorrelation and multi-regression techniques, severalestuarine processes could be identified which dominateand/or control the behaviour of the individual tracemetals in three distinct areas of the Scheldt estuary. The behaviour of the four selected metals was foundto show some common features, but is besides this alsocharacterised by many individual and specificproperties. The total metal concentrations seem toco-vary well with the turbidity in the maximumturbidity zone between salinities 2 and 10 psu. In thedownstream area a dilution profile is observed for thetotal metal concentrations of Cu and Cd as well as forthe dissolved concentrations of all metals. Dissolved metal production rates are high for Cu andCd, but much lower for Zn and Pb, confirming thedifferent longitudinal dissolved metal profiles. ForCu and Cd these dissolved metal profiles arecharacterised by a broad mobilisation area, coveringthe whole middle estuary. Pb on the other hand, showsa more confined mobilisation area, and for Zn no sucharea was found. During winter the dissolved metalproduction rates seem to be controlled, predominantly,by desorption processes. During summer dissolved metalproduction is correlated mainly to the dissolvedoxygen content, suggesting the domination of redoxprocesses solely or in combination with desorptionprocesses. In some cases, co-existent with nearly zerooxygen concentrations, removal of dissolved metals wasobserved, possibly reflecting precipitation reactions. Longitudinal particulate metal profiles all show anegative deviation versus the dilution profile. Cu andCd provide the higher deviations, characterised by anarrow enrichment zone preceding a broad mobilisationarea. Finally, all particulate metal profiles appearedto correlate well with POC, when expressed involumetric units. This revised version was published online in July 2006 with corrections to the Cover Date.     

Overview of trace metal contamination in the Scheldt estuary and effect of regulatory measures

Seasonally, dissolved and particulate metal concentrations in the Scheldt estuary were assessed over a period of 4 years (1995–1998). High quality data were obtained following stringent analytical protocols for each step: sampling, sample treatment, sample storage and analysis. Of the 5 trace metals, Ni showed the most conservative behaviour, while Cd and Cu were clearly transferred from the particulate to the dissolved phase in the middle estuary. A substantial part of the particulate metals entering the estuarine system are lost through sedimentation. General seasonal patterns are the following: lower concentrations in spring and higher ones in winter (sometimes late fall/early winter) for dissolved metals, while in summer a pronounced rise of the longitudinal concentration profile is observed for the particulate metals. A comparison of the trace metal concentrations (dissolved and particulate) at the mouth of the estuary in 1995–1998 with those from 1981 to 1983, reveal reductions between 30 and 58%. Reductions based on direct emission measurements for almost the same period suggest reductions (dissolved + particulate) between 42 and 64%. Biomagnification (BMF) is the accumulation of a compound through the food-chain. It is in our case expressed as the ratio of the metal concentration in the organism (g g^–1, d.w.)/the metal concentration in total suspended matter (g g^–1, d.w.). Almost all BMF-values of Periwinkle, Nereis diversicolor and Macoma balthica (3 bottom organisms in the Scheldt estuary) are negative meaning that these organisms contain less heavy metals than the particulate suspended matter. For all organisms log BMFs for Pb, respectively Ni, are around –1.8, respectively –0.7. For Cd, Periwinkle shows slight enrichment (0.05) and for Cu even more (0.45), while negative values were observed for Nereis diversicolour and Macoma balthica. The latter organisms are more enriched in Zn (–0.09) than Periwinkle (–0.43).     

The role of phytoplankton in pollutant transfer processes in rivers. Example of River Marne (France)

The impact of the spring phytoplanktonic blooms on the partition of nutrients and metals between the dissolved and particulate phases was studied over two years in the river Marne, upstream of its confluence with the river Seine. Particular attention was devoted to copper and manganese, determined in the dissolved phase (< 0.22 m), subdivided into the colloidal phase and the 'truly dissolved' phase (< 10 KDaltons) obtained by tangential ultrafiltration. During the algal growth peaks, a sharp reduction of nutrients was observed in the dissolved phase: in 1994, consumption of 70% of silica, 50% of ammonium and 40% of soluble phosphorus present before the phytoplanktonic bloom.The water concentration peaks of suspended matter (SM) and of particulate metals, phosphorus and carbon coincide with those of chlorophyll. The highly significant correlations between pH and chlorophyll (r = 0.92, P < 0.001), pH and SM (r = 0.97, P < 0.001) and chlorophyll and SM (r = 0.93, P < 0.001) confirmed the phytoplanktonic nature of SM and the determining role of pH in the partition of metals, its increase being responsible for the coprecipitation of metal. As a corollary to the increase in the particulate phase, a decrease of 55% was observed for copper and manganese in the 'truly dissolved' phase compared to the concentrations outside bloom periods.The importance of the colloidal fraction was also shown. During the strong algal growth periods, the proportion of 'colloidal metal' in the dissolved phase (< 0.22 m) reached 60% and the increase in the colloidal fraction was 4 times stronger for copper than for manganese. While manganese seemed to be more associated with macroparticles, copper was more associated with fine colloidal biological particles intrinsic to the phytoplankton.     

Elemental composition of seston and nutrient dynamics in the Sea of Marmara

The Sea of Marmara, an intercontinental basin with shallow and narrowstraits, connects the Black and Mediterranean Seas. Data obtained during1991–1996 have permitted the determination of the elementalcomposition of seston in the euphotic zone and the N:P ratio of thesubhalocline waters of the Marmara Sea. Since primary production is alwayslimited to the less saline upper layer (15–20 m), of the Marmara Sea,the subhalocline waters of Mediteranean origin are always rich in nutrients(NO₃ + NO₂ = 8–10 μm, PO₄ = 0.8–1.2 μm) but depleted in dissolvedoxygen (30–50 μm) throughout the basin, yielding an -O_{_2} : N : P ratio of 178 : 9 : 1. Pollution of the surfacewaters since the 60s has modified the subhalocline nutrient chemistryslightly. In the euphotic zone, the N : P ratio of the seston changes from5.9 to 9.5 between the less and more productive periods. Though the biologyof the Marmara has changed significantly during the previous two decades,the close relationship observed between the elemental composition of thesurface seston and the NO₃ : PO₄ ratio of thesubhalocline waters strongly suggests that during the whole year primaryproduction throughout the basin and POM export to the lower layer remainnitrogen-limited. This suggestion needs to be confirmed by bio-assays,biological studies and sediment trap data from the upper subhaloclinedepths. Nonetheless, the counterflows in the Marmara basin possessrelatively low N : P ratios in both dissolved and particulate nutrients andextend as far as the adjacent seas. This revised version was published online in July 2006 with corrections to the Cover Date.     

Biogeochemistry and effects of copper,manganese and zinc added to enclosures in Island Billabong,Magela Creek,northern Australia

Three large plastic enclosures (5 m diam, volume 40 m³) were used to study the effects of copper, manganese and zinc, on the phytoplankton community in Island billabong, a floodplain billabong (waterhole) situated in the Magela Creek in tropical northern Australia. Copper was added to one enclosure, and manganese and zinc to another, to give initial concentrations around ten times the normal wet season values. The enclosures and the billabong were monitored over a ten week period towards the end of the dry season, with the enclosures allowed to stabilise for four weeks before the metals were added.The control enclosure adequately simulated the temperature and pH changes in the billabong. The trends in conductivity, dissolved oxygen and major ion concentrations were similar in the enclosure and the billabong, with the minor differences observed attributed to either epiphytic growth on the enclosure walls (influenced dissolved oxygen, pH and bicarbonate concentration) or ingress of sulphate-rich groundwater into the billabong (influenced sulphate concentration and conductivity). Major differences in both the composition of species and the size of the phytoplankton populations were observed between the three enclosures and between the control enclosure and the billabong. This variability reflects the great natural variability in the phytoplankton communities in tropical lentic systems, and means that enclosures are unlikely to adequately simulate the biological communities in the billabongs.The control enclosure appeared to simulate quite well the longer term changes in total concentration and speciation of the three metals (copper, manganese & zinc) in the billabong. The mean concentrations of copper and zinc were similar in the two systems, although the mean concentration of manganese in the billabong was almost double that in the enclosure, possibly due to ingress of manganese-enriched groundwater. Particulate forms dominated the speciation of copper and manganese. There was considerable short term variation in both total metal concentration and speciation in both the enclosure and the billabong. This variability appears to be a feature of these small tropical waterbodies.The added heavy metals were found to have minimal detrimental effect on the phytoplankton community in each metal-loaded enclosure. The high natural variability in the phytoplankton community in these tropical systems will make it difficult to separate natural changes from those caused by low level contamination from mining operations should this occur.All three metals were rapidly removed from the water column, so that by the end of the six week period, only ca. 5% of each added metal remained in the water column. Association with the particulate matter (phytoplankton, abiotic particulate matter and MnO_x in enclosure 2) followed by sedimentation was the major removal pathway. Epiphytes growing on the enclosure walls appeared to have a minor influence (<10% of the total amount of metal added) on the removal of the added metals. For copper, uptake by phytoplankton followed by sedimentation was the major (65%) removal process. Manganese and zinc, added together, were found to influence each other. The major manganese removal process (60%) was rapid (ca. 3 days) involving bacterial oxidation and sedimentation of the MnO_x formed. This material appeared to have little influence on the behaviour of zinc, possibly because other particulate matter competed more effectively for the zinc. A further 30% of the added manganese was removed via initial adsorption to other particulate matter, possibly phytoplankton. Approximately one third of this adsorbed manganese (10% of the total added) appeared to undergo delayed oxidation some 8 days after the initial additions, and the heavier particles settled out more rapidly. This path was responsible for removing the major amount (ca. 60%) of the added zinc. We hypothesis that the sorbed zinc inhibited the bacterial oxidation of the manganese. A further 25% of the zinc was removed in association with a burst of phytoplankton activity. The occurrence of bursts in the phytoplankton activity, when populations can increase very substantially and then decrease again, all within the space of a day, appears to be an important mechanism for removing copper and zinc from the water column in these tropical water bodies     

Application of in situ cage cultures of phytoplankton for monitoring heavy metal pollution in two Norwegian fjords

A simple apparatus for in situ use of the cage culture technique for growing planktonic algae has been developed and used to follow growth and metal uptake of three diatoms in two Norwegian fjords polluted by heavy metals. Continuous pumping of sea water through a chelating resin and continuous water sampling was used to obtain average values for dissolved and particulate heavy metal content at the various test sites. The metals investigated (zinc, copper, lead, cadmium, and mercury) showed differences in the proportion of dissolved to particulate fractions.The three species of diatoms tested gave systematic growth responses to heavy metal pollution in the moderately polluted fjord; one alga died, one showed reduced growth rate at the more contaminated site compared with those at less polluted sites, while the most tolerant alga was apparently not affected. In the heavily polluted fjord only the most tolerant alga survived, showing decreasing growth rate with increasing pollution.Uptake of heavy metals increased generally with increasing heavy metal content in the sea water. The contents in the algae grown in the most polluted fjord were much higher than those obtained in the less polluted fjord, which were higher than the contents reported for algae from non-contaminated areas.     

Larval development of hermit crab Clibanarius longitarsus: Synergistic effect of heavy metals

The levels of heavy metals copper and zinc were found to be high in the Vellar estuary. Therefore their effects on the larval development of the abundant hermit crab Clibanarius longitarsus were studied individually and in combination from hatching till moulting to glaucothoe stage in the laboratory using freshly hatched Artemia nauplii as food. The 96 h LC50 values found with 100 larvae each kept in 10 different concentrations of copper and zinc (350, 300, 250, 200, 150, 100, 50, 25, 10 and 5 ppb) were 50 ppb for copper and 90 ppb for zinc. Based on these 96 h LC50 values, three sublethal concentrations were chosen for the metals copper and zinc at 50%, 25% and 10% levels of the LC50 values. With increase in concentration of the test medium, the survival rate decreased and the time required for the completion of each zoeal stage increased. Copper was found to be more toxic than zinc as the survival rate in copper concentrations was lower than those in zinc concentrations. The survival rate in the mixed concentrations of metals was lower than in individual concentrations.     

Pollution of a Tasmanian River by Mine Effluents I. Chemical Evidence

Discharge of effluents from tin and wolfram mines has caused severe pollution of two creeks and lesser pollution of the South Esk River in North-East Tasmania. The principal pollutants are sulphuric acid, zinc, cadmium, copper, lead, iron and manganese in dissolved or particulate form or both. The creek waters are rendered unsuitable for domestic or agricultural use and all normal biota destroyed. In the South Esk River trout are absent from polluted reaches though abundant elsewhere. Flood-borne mine tailings, rich in particulate pollutants, have destroyed or degraded pastures along the South Esk River.     

Quantification of toxic and inhibitory impact of copper and zinc on mixed cultures of sulfate-reducing bacteria

The adverse effects of copper and zinc on an acetate-utilizing mixed cultures of sulfate-reducing bacteria (SRB) at concentrations below the toxic concentration (minimum metal concentration at which no sulfate reduction is observed) are reported in this paper. Mathematical models were developed to incorporate the toxic and inhibitory effects (defined as the reduction in bacterial population upon exposure to the metal and the decrease in the metabolic rate of sulfate reduction by the SRB, respectively) into the sulfate-reduction biokinetics. The characteristic toxicity and inhibition constants were obtained from the measurements of bacterial populations and dissolved metal concentrations in serum bottle studies conducted at 35 degrees C and pH 6.6. Both copper and zinc had toxic and inhibitory effects on SRB. The toxicity constants for copper and zinc were 10.6 and 2.9 mM(-1), respectively, indicating that exposure to copper resulted in a higher mortality of SRB than did exposure to zinc. The values of the inhibition constants were found to be 17.9 +/- 2.5 and 25.2 +/- 1.0 mM(-1) for copper and zinc, respectively. This implies that dissolved zinc was slightly more inhibitory to SRB than copper. The models presented in the paper can be used to predict the response of a sulfate-reduction bioreactor to heavy metals during acid mine drainage treatment.     

Comparative strategies of heavy metal accumulation by crustaceans: zinc,copper and cadmium in a decapod,an amphipod and a barnacle

This study investigates the comparative strategies of accumulation under standardised laboratory conditions of the essential metals zinc and copper, and the non-essential metal cadmium by three crustaceans of different taxa; vizPalaemon elegans Rathke (Malacostraca: Eucarida: Decapoda),Echinogammarus pirloti (Sexton & Spooner) (Malacostraca: Peracarida: Amphipoda) and the barnacleElminius modestus Darwin (Cirripedia: Thoracica).The decapodP. elegans regulates body zinc concentrations to a constant level (ca. 79 µg Zn g^–1) over a wide range of dissolved metal availabilities until regulation breaks down at high Zn availabilities and net accumulation begins. The amphipodE. pirloti accumulates zinc at all dissolved zinc concentrations but at a low net rate such that the accumulation strategy approaches that of regulation. The barnacleE. modestus accumulates zinc to high body concentrations with no significant excretion of accumulated zinc. In the case of copper,P. elegans similarly regulates body copper concentrations to a constant level (ca. 129 µg Cu g^–1) over a range of dissolved copper availabilities until regulation breaks down at high copper concentrations. Both the amphipodE. pirloti and the barnacleE. modestus on the other hand accumulate copper at all dissolved copper exposures with no evidence of regulation. All three crustaceans accumulate the non-essential metal cadmium at all dissolved cadmium concentrations without regulation.Heavy metal accumulation strategies therefore vary between crustacean taxa and between metals. Uptake rates for zinc and cadmium have been estimated for the three crustaceans and can be interpreted in terms of cuticle permeability and way of life of each crustacean. Examination of these uptake rates provides an insight into possible reasons behind the adoption of particular metal accumulation strategies.     

An Ecological Risk Assessment of Air Emissions of Trace Metals from Copper and Zinc Production Facilities

Trace metals are components of releases to air emitted by copper and zinc production facilities in Canada. Six metals (copper, zinc, nickel, lead, cadmium, and arsenic) are examined as part of an overall environmental assessment of these releases. Estimates of metal deposition rates to soils and surface waters were derived from monitoring data in the vicinity of the production facilities and also through dispersion modelling studies. Fate and transport modelling of the metals deposited allowed an estimation of critical loads. Estimated annual deposition rates were compared with 25^th-percentile critical loads typically representative of effects on sensitive organisms under 25% of conditions in sandy soils or circumneutral to acidic lake waters. The results of the comparison suggest that there is a potential for adverse effects on aquatic and/or soil-dwelling organisms from exposure to steadystate concentrations of metals in the vicinity of copper and zinc production facilities. Approaches of particular significance in these assessments include probabilistic estimation of critical loads for metals, allowance for the speciation of metals defining the bioavailable fraction and limiting critical effect levels to the high end of natural background metal concentrations.     

Synthesis of TPEN variants to improve cancer cells selective killing capacity

TPEN is an amino chelator of transition metals that is effective at the cellular and whole organism levels. Although TPEN of often used as a selective zinc chelators, it has affinity for copper and iron and has been shown to chelate both biologically. We have previously shown that TPEN selectively kills colon cancer cells based on its ability to chelate copper, which is highly enriched in colon cancer cells. The TPEN-copper complex is redox active thus allowing for increased ROS production in cancer cells and as such cellular toxicity. Here we generate TPEN derivatives with the goal of increasing its selectivity for copper while minimizing zinc chelation to reduce potential side effects. We show that one of these derivatives, TPEEN despite the fact that it exhibits reduced affinity for transition metals, is effective at inducing cell death in breast cancer cells, and exhibits less toxicity to normal breast cells. The toxicity effect of the both chelators coupled to the metal content of the different cell types reveals that they exhibit their toxicity through chelating redox active metals (iron and copper). As such TPEEN is an important novel chelators that can be exploited in anti-cancer therapies.     

The environmental risks of pollution in the Scheldt estuary

The ecotoxicological effects of pollution in the Scheldt estuary is evaluated for several routes of exposure by comparing observed concentrations of micro-contaminants in water and tissues of biota with toxicity data in literature. Ecological risks are estimated for dissolved trace metals according to the method of VAN STRAALEN (1990) using published data on NOECs from aquatic toxicity tests concerning reproduction, mortality and growth for cold blooded marine and estuarine organisms. Of eight investigated trace metals, zinc and nickel cause the highest risks, both affecting up to 4% of the aquatic species. The occurrence of bioaccumulation of PCBs and cadmium is investigated in several trophic levels. High concentrations of PCBs are observed in tissues of biota and may indicate adverse effects on top predators (seals, terns), especially in the brackish zone. Environmental risks of other organic micro-contaminants have not been indicated due to the limited number of data on toxicity or environmental concentrations. The effects of a mixture of pollutants in sediments from the Scheldt estuary were investigated with an oyster larvae bioassay showing an increased toxicity in upstream direction. Moreover, in the upper part of the estuary, preconditions regarding the oxygen concentration are not met and overshadow the toxic effects of pollution with micro-contaminants. Especially in the less contaminated part of the estuary more ecotoxicolgical research is required to perform an integral risk evaluation. At present, still little is known about effects that may occur in the field.     

Dissolved and particulate trace metal geochemistry in the scheldt estuary,S. W. Netherlands (water column and sediments)

The geochemistry of dissolved and particulate trace metals has been studied in the water column and the sediments of the Scheldt estuary between 1987 and 1990. A strong seasonal influence on the behaviour of dissolved Cd, Cu and Zn is observed, related to the redox conditions in the upper estuary and phytoplankton activity in the lower estuary (which are both seasonally dependent variables). The dissolved trace metal concentrations in the fresh water end-member are remarkably low during spring and summer, due to metal sulphide precipitation in the anoxic Scheldt river. However, the dissolved concentrations increase rapidly with increasing salinity, due to oxidation of metal sulphides that are present in the suspended matter, accompanied by (e.g. chloro-)complexation of the released metals. Readsorption of Cd and Zn occurs in the lower estuary during the spring phytoplankton bloom. During winter, when the Scheldt river is not completely anoxic, much higher dissolved trace metal concentrations are observed in the fresh water end-member since metal sulphide precipitation in the water column is precluded. Rapid trace metal removal is observed in the low salinity, high turbidity zone, due to adsorption onto suspended matter and freshly precipitated iron and manganese oxyhydroxides. Upon further mixing, desorption is apparent, due to a similar oxidation-complexation mechanism as observed during spring and summer. Pore water infusion may also contribute to the enrichment of dissolved Cd, Cu and Zn in the mid-estuarine region. The trace metal contents of the suspended matter and the sediments show a continuous decrease with increasing salinity. This behaviour is to a very large extent due to physical mixing of contaminated fluvial particulates and relatively unpolluted marine particulates. Desorption of Cd, Cu and Zn can be identified but is of minor importance compared to the conservative mixing process. The distribution of dissolved Cd, Cu and Zn in the pore waters of the mid-estuarine region reflects the impact of early diagenetic processes. Trace metal peaks are observed near the sediment-water interface, and at greater depth in the manganese and iron reduction zones. These peaks are attributed to oxidation of reduced trace metal compounds (e.g. sulphides) and reduction of the (iron and manganese) oxide carrier phases, respectively. At greater depth, the dissolved trace metal concentrations are much lower due to metal sulphide precipitation in the sulphate reduction zone. Analysis of a large sediment dataset indicates severe trace metal pollution of the Scheldt estuary at the end of the fifties. A major reduction of the pollution by As, Cr, Hg, Pb, and Zn has occurred in the seventies, and of Cd and Cu in the eighties. The Ni pollution has increased over the time period considered. In spite of this improvement, the present-day pollution status of the Scheldt estuary is still reason for concern.     

Benthic phosphorus regeneration in the Potomac River Estuary

The flux of dissolved reactive phosphate from Potomac riverine and estuarine sediments is controlled by processes occurring at the water-sediment interface and within surficial sediment.In situ benthic fluxes (0.1 to 2.0 mmoles m⁻² day⁻¹) are generally five to ten times higher than calculated diffusive fluxes (0.020 to 0.30 mmoles m⁻² day⁻¹). The discrepancy between the two flux estimates is greatest in the transition zone (river mile 50 to 70) and is attributd to macrofaunal irrigation. Bothin situ and diffusive fluxes of dissolved reactive phosphate from Potomac tidal river sediments are low while those from anoxic lower estuarine sediments are high. The net accumulation rate of phosphorus in benthic sediment exhibits an inverse pattern. Thus a large fraction of phosphorus is retained by Potomac tidal river sediments, which contain a surficial oxidized layer and oligochaete worms tolerant of low oxygen conditions, and a large fraction of phosphorus is released from anoxic lower estuary sediments. Tidal river sediment pore waters are in equilibrium with amorphous Fe (OH)₃ while lower estuary pore waters are significantly undersaturated with respect to this phase. Benthic regeneration of dissolved reactive phosphorus is sufficient to supply all the phosphorus requirements for net primary production in the lower tidal river and transition-zone waters of the Potomac River Estuary. Benthic regeneration supplies approximately 25% as much phosphorus as inputs from sewage treatment plants and 10% of all phosphorus inputs to the tidal Potomac River. When all available point source phosphorus data are put into a steady-state conservation of mass model and reasonable coefficients for uptake of dissolved phosphorus, remineralization of particulate phosphorus, and sedimentation of particulate phosphorus are used in the model, a reasonably accurate simulation of dissolved and particulate phosphorus in the water column is obtained for the summer of 1980.     

Hepatic zinc,copper, and iron in the developing turkey embryo and newly hatched poult

The ontogeny of hepatic tissue growth and trace metal deposition was examined in the developing turkey embryo and newly hatched poult. Hepatic concentrations of zinc and iron in the embryo declined by about twofold between day 16 of incubation and hatching. Hepatic copper concentration increased approximately fourfold by day 23 of incubation and then declined rapidly through hatching. During the post-hatching period, hepatic zinc concentration increased twofold by day 10, whereas a small increase in hepatic iron concentration occurred just prior to hatching and continued through the third day post-hatching. A significant positive correlation existed between hepatic zinc and iron concentrations in the developing embryo. The concentrations of both these metals were inversely correlated with hepatic copper concentration during the same time. Total hepatic zinc and iron content increased throughout the entire time studied, whereas total copper content increased up to hatching and then declined during the first week post-hatching. The most rapid phase of hepatic metal accretion differed for each metal, with zinc being rapidly accumulated during the post-hatching period, copper during the last half of incubation and iron at about the time of hatching and the first few days post-hatching. Each of these metals demonstrated a specific relationship to hepatic tissue growth that changed between the embryonic and neonatal periods of development.     

Calculation of the Ecological Risk Index in the José Antonio Alzate Dam, State of Mexico, Mexico

Due to the problem of contamination in the Jose Antonio Alzate dam, located in the State of Mexico, Mexico, the partition coefficient, the contamination degree, and the ecological risk index of nine metals were calculated in order to establish the water quality in different areas of the Alzate dam. The sampling sites were selected according to the river flow into the dam, via three sampling programs, the physical–chemical parameters were measured in situ, and the samples were collected to measure metals in the dissolved phase and also as suspended particulate matter. Thomann’s model was used to calculate the partition coefficient. Håkanson’s methodology was used to determine the degree of contamination and the ecological risk index. Finally, the water quality criteria for the dissolved metals were calculated. The results for suspended particulate matter suggest a moderate risk of metal contamination in the dam. Copper and lead in dissolved form exceeded the values of water quality criteria.     

Suspended particulate oxides and organic matter interactions in trace metal sorption reactions in a small urban river

The relative scavenging abilities of suspended particulate oxides (SPOX), and organic matter (SPOM) for Cd, Zn and Cu were evaluated in a small, anthropogenically influenced river. In addition, the factor most important in influencing the sorption density (A_d: metal concentration associated with a given phase divided by the concentration of that geochemical phase in the suspended particulate pool) of each metal to SPOX and SPOM were identified through multiple linear regression analyses from the suite of: pH, temperature, dissolved metal concentration, and the concentration of the other particulate fraction. Results indicate that SPOX-SPOM interactions do occur in trace metal complexation reactions; and interactions are both phase and cation specific. Fe oxides are able to outcompete discrete organic binding sites for Cu and Zn as a relative decrease in the amount of these two cations sorbed to organic matter was observed with increasing particulate Fe oxides. SPOM concentration was identified as being most important in influencing Cu sorption densities associated with the SPOX fraction. Organic matter — oxide complexes are postulated to occur that enhance oxide sorption of Cu such that relatively more Cu is sorbed to particulate oxides with increasing particulate organic matter concentrations. Dissolved concentrations of Cd and Zn were found to be most important in influencing the sorption densities for these two metals associated with the oxides fraction. The sorption behaviour appears to follow Freundlich isotherm behaviour where the amount sorbed is a function of the dissolved concentration.     

Multilevel Anthropogenic Cycles of Copper and Zinc: A Comparative Statistical Analysis

Contemporary cycles for copper and zinc are coanalyzed with the tools of exploratory data analysis. One-year analyses (circa 1994) are performed at three discrete spatial levels-country (52 countries that comprise essentially all anthropogenic stocks and flows of the two metals), eight world regions, and the planet as a whole-and are completed both in absolute magnitude and in per capita terms. This work constitutes, to our knowledge, the first multiscale, multilevel analysis of anthropogenic resources throughout their life cycles. The results demonstrate that (1) A high degree of correlation exists between country-level copper and country-level zinc rates of fabrication and manufacturing, entry into use, net addition to in-use stocks, discard, and landfilling; (2) Regional-level rates for copper and zinc cycle parameters show the same correlations as exist at country level; (3) On a per capita basis, countries add to in-use stock almost 50% more copper than zinc; (4) The predominant discard streams for copper and zinc at the global level are different for the two metals, and relative rates of different loss processes differ geographically, so that resource recovery policies must be designed from metalspecific and location-specific perspectives; (5)When absolute magnitudes of life-cycle flows are considered, the standard deviations of the data sets decrease from country level to regional level for both copper and zinc, which is not the case for the per capita data sets, where the statistical properties of the data sets for both metals approach being independent of spatial level, thus providing a basis for predicting unmeasured per capita metal flow behavior.